CHAPTER 3 PERIODIC CLASSIFICATION www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116 CHAPTER 3 PERIODIC CLASSIFICATION

EARLIER ATTEMPTS OF CLASSIFICATION OF ELEMENTS 1. Doberenier’s Triads 2. Newland’s Law of Octaves 3. Mendeleev’s Periodic Table 4. Long form of Periodic Table www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Doberenier’s Triads Certain similar elements exist in group of three elements which he named as triads. The At. Wt. of middle member was the arithmetic mean of the other two members of the triad. Properties of the middle element was intermediate of the other two. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Newland’s Law of Octaves Elements were arranged in increasing order of atomic weights. Eight element, starting from a given one is a kind of repetition of the first. – like musical notes www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Mendeleev’s Periodic Table “The properties of elements are a periodic function of their atomic weights”. Main criterion of the judgment of similarities in the properties was valency of the elements. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

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Modern Periodic Law The physical & chemical properties of the elements are the periodic function of their atomic numbers. Cause of Periodicity: The periodic repetition is due to the recurrence of similar valence shell configurations after certain regular intervals. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Long form of Periodic Table www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

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About Periodic table No. of periods: 7 No. of Groups: 18 No. of periods represents the highest principal quantum number (n) of the elements present in it. First Period: n=1…..(1s) two elements (h & He) Second Period n=2….(2s & 2p) eight elements (Li to Ne) Third Period n=3 …(3s & 3p) eight elements (Na to Ar) Fourth Period n=4 …(4s, 3d & 4p) eighteen elements (K to Kr) Fifth Period n=5…(5s, 4d & 5p) eighteen elements (Rb to Xe) Sixth Period n=6…(6s, 4f, 5d & 6p) thirty two elements (Cs to Rn) (Lanthanoids …Ce to Lu)….14 elements (4f) Seventh Period n=7…(7s, 5f, 6d, 7p) (Actinoids…Th to Lr) www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

About Periodic table Period no. 2 & 3 are called ………..Short Periods Period no. 4 & 5 are called ………..Long Periods Period no. 6 is called ………………Longest Period www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

s-block elements (ns1-2) Also known as representative elements or main group elements “When last electron enters s-subshell, it is an s-block element.” Gr. 1: Alkali metals, Gr. 2: Alkaline earth metals Properties of s-block elements: Low IE, High e-+ve character. Very reactive & hence do not occur in native state. Good reducing agents Compounds are predominantly ionic www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

p-Block elements (ns2np1-6) Also known as representative elements or main group elements “The elements in which the last electron enters the p- subshell of their outermost energy level are called p- block elements” Exhibit variable oxidation states They form ionic as well as covalent compounds They have relatively high values of IE Most of them are non-metals, highly electronegative, form acidic oxides. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

d-Block elements [(n-1)1-10ns2] “The elements in which the last electron enters the d-subshell of their outermost energy level are called d-block elements” They Are Hard, high Melting metals, Have Variable oxidation states Form coloured complexes Form ionic as well as covalent compounds Most of them exhibit paramagnetism, possess catalytic properties Form alloys, Are good conductors of heat & electricity www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

f-Block elements [(n-2)f1-14(n-1)d0-10ns2] Also known as inner transition elements or f-transition elements (Lanthanoids & Actinoids) “The elements in which the last electron enters the f- subshell of their outermost energy level are called f- block elements” They Show variable oxidation states Have high MP, high densities Form complexes, most of which are coloured Most of the actinoid series are radioactive. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Atomic Radius “The distance from the centre of nucleus of the atom to the outermost shell of electrons.” 1. Covalent Radius: One-half of the distance between the centres of the nuclei of two similar atoms bonded by a single covalent bond. 2. Metallic Radius: One-half of the internuclear distance between two adjacent atoms in the metallic lattice. ***The metallic radius is always larger than its covalent radius. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Variation of atomic radius Increases down the group Decreases across the period. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

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Ionic radius “Ionic radius is defined as the effective distance from the nucleus fo the ion to the point up to which it has an influence in the ionic bond” (a) The size of cation is smaller than parent atom becoz of increase in the effective nuclear charge per electron. (b) The size of anion is greater than parent atom becoz of decrease in effective nuclear charge per electron. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Ionization Enthalpies “The amount of energy required to remove the most loosely bound electron from its isolated gaseous atom in the ground state” www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Ionization Enthalpy depends on… 1. Size of atom Decreases with the increasing size of atom as the electrons are less tightly held with increasing distance 2. Magnitude of nuclear charge Higher the nuclear charge, higher the IE. 3. Screening effect of the inner electrons (Outermost electrons are shielded or screened by the inner electrons. This is screening effect.) IE decreases with increase in screening effect. More the no. of inner electrons, greater is the screening and lower is the IE. 4. Penetration effect of the electrons: Penetration effect for a given ‘n’ s>p>d>f. Greater the penetration, lower the shielding by other electrons, higher the IE. 5. Electronic configuration: Atom having more stable (half filled, fully filled subshells) config. has less tendency to lose e-, hence higher the IE. noble gases (ns2np6) elements like N: [He] 2s22px12py12pz1 & P: [Ne] 3s23px13py13pz1 have half-filled stable configuration. elements like Be: 1s22s2, Mg:[Ne]3s2 have electrons paired www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Variation of IE across the period IE across the period increases due to.. 1. Increase in Nuclear charge 2. Addition of e-s in the same energy level 3. Decrease in atomic size. Exceptions: 1. Decrease from Be to B: Reason: (a) penetration of 2s>2p (b) more shielding faced of 2p by inner electrons (c) more stable config of Be. 2. Decrease from N to O: Relatively stable half-filled configuration of N: [He] 2s22px12py12pz1. 3. Large increase from F to Ne: Fully-filled energy level of Ne. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Variation of IE down the group IE decreases in general down the group due to.. 1. addition of new energy levels 2. increase in screening effect. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Electrongain enthalpies “The enthalpy change taking place when an isolated gaseous atom of the element accepts an electron to form a monovalent gaseous anion” X(g) + e- → X-(g) Larger the negative EGE, greater the tendency to accept electron. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Factors affecting EGE 1. Nuclear charge: Greater the NC, more attraction, large –ve is the EGE 2. Atomic size: Smaller the size, higher the attraction, large –ve is the EGE 3. Electron configuration: More stable e- configuration, less tendency to accept the e-, less –ve EGE. For example: Noble gases have high +ve EGE. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Variation of EGE across the period Across the period, atomic size decreases & nuclear increases, therefore electron gain enthalpies tend to be more –ve. Some irregularities… 1. in group 2 → filled ns subshells 2. in group 15 → half-filled np subshells 3. in group 18 → fully filled subshells These elec config are relatively stable & hence these have +ve or very low –ve EGEs. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Variation of EGE down the group Down the group, the atomic size & nuclear charge both increase. But increase in atomic size is more pronounced. Therefore, EGE becomes less –ve down the group. Some irregularities… 1. F(-328) < Cl(-349). Reverse expected. Becoz, when an electron is added to F, it goes to relatively compact n=2 energy level. As a result it experiences significant e-e repulsion. 2. Same is the case with O(-141) < S(-200). www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Successive EGE X(g) + e- → X-(g) ∆egH1 X-(g) + e- → X-2(g) ∆egH2 Always, ∆egH2 is +ve . This is becoz, when e- is added to uninegative ion, it experiences significant repulsion. Hence energy has to be supplied to overcome the repulsive force to add electron. Hence values of successive EGEs are positive. For example: O(g) + e- → O-(g) ∆egH1 =-141kJ O-(g) + e- → O-2(g) ∆egH2 =+780kJ www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Electronegativity “The tendency of an atom in a molecule to attract the shared pair of electron towards itself” Factors affecting electronegativity are… 1. Effective nuclear charge Greater the Nuclear charge, greater is the EN 2. Atomic radius smaller the Atomic radius, greater the EN ***EN for any given element is not constant but varies depending on the element to which it is bound. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Variation of EN Increases across the period… becoz of increasing nuclear charge and decreasing atomic size. Decreases down the group… becoz of increasing atomic size. ------------------------------------------------- *** non-metallic character is directly related to EN. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

electronegativity www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Electropositivity or metallic character “ Tendency of atoms of an element to lose electrons and form +ve ions is known as Electropositivity” A more electro+ve element has more metallic character. Variation of Electropositive character… Decreases across the period due to increase in IE Increases down the group due to decrease in IE www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

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Valence “ The valence of an element may be defined as the combining capacity of element ” Valence= no. of H or Cl or double the no. of O atoms that combine with an atom of an element. Electrons present in the outermost shell are called valence e-s. Down the group, the valency remains the same. Across the period, increases from 1to 4 & then decreases from 4 to 0. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

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Nature of oxides 1. Oxides of elements at the extreme left of periodic table are BASIC in nature. (metallic oxides) 2. Extreme right, ACIDIC. (non-metallic oxides) 3. A Basic oxide is one which when dissolves in water gives a base. Na2O + H2O → 2NaOH Basic oxide Base 4. An Acidic oxide is one which when dissolved in water gives an acid Cl2O7 + H2O → 2HClO4. Acidic oxide Acid www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Contd… 5. An Amphoteric oxide exhibits acidic behaviour in presence of base and basic behaviour in presence of acid. Al2O3 + 6HCl → 2AlCl3 + 3H2O Al2O3 + 2NaOH → 2Na[Al(OH)4] 6. A Neutral oxide exhibits neither acidic nor basic properties. * Since metallic character increases down the group, the basic character of oxides also increases. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Anomalous properties of second period “ First member of each group (from Li to F) is different from rest members of the same group” For example: Li → covalent compounds while other members of group 1 → ionic compounds Reason: 1. Small size of the first element 2. Large charge/radius ratio 3. High EN 4. Absence of d-orbitals in the valence shell of the first element: 1st element → n=2, no d-orbitals in this energy level ∴ no d- orbitals available ∴ maximum covalency =4 On the other hand, n=3 onwards d-orbitals are available. ∴ covalency can be expanded beyond 4. 5. Ability to form pπ-pπ multiple bonds: 1st member due to its small size, forms pπ-pπ multiple bonds with itself & other members of 2nd period. eg: C=C, C≡C, C=O, C ≡N. Other members do no form pπ-pπ bonds due to their larger sizes. www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

Diagonal Relationship “ An element of the 2nd period exhibits certain similarities with the 2nd element of the following group ” For example: 1 2 13 14 Li Be B C Na Mg Al Si “ Diagonal relationship is the similarity between a pair of elements in different groups and different periods and located diagonally in the periodic table” www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116

End of chapter www.chemzblog.wordpress.com.....Zaid Mansuri 9824662116